CN108473780A - Conductive composition, its manufacturing method and conductive material - Google Patents

Abstract

Even if the issue of the present invention is to provide when a kind of situation calcined under air, the conductive composition for the conductive film for showing good electric conductivity and humidity resistance can be also formed.The conductive composition of the present invention contains is attached with the surface treatment copper powders (AB) of ascorbic acid derivates (B), adhesive resin (C) and dispersant (D) with acidic groups on the surface of copper powder (A).Utilize conductive composition to solve the problem.

Description

Conductive composition, its manufacturing method and conductive material

Technical field

The present invention relates to a kind of conductive composition and its manufacturing methods.In turn, the present invention relates to one kind have base material and The conductive material of conductive film, the conductive film are the dried object or hardening thing of conductive composition.

Background technology

Forming method as electronic component, the film forming method of conductive sheet timber-used or conducting channel, it is known that etching Method and print process.Etching method obtains the circuit diagram of required shape to remove a part for metal envelope by using etching solution The method of case, but usually step is miscellaneous, and liquid waste processing is separately needed, therefore have the problem of expense or carrying capacity of environment.In addition, utilizing erosion It is to be formed, therefore do not tolerate the physical impacts such as bending etc. to ask by metal materials such as aluminium or copper etc. that lithography, which is formed by conducting channel, Topic.

Therefore, conducting channel is inexpensively formed in order to solve these problems and more, and conductive paste, which receives, to be gazed at.Pass through printing Conductive paste can easily form conducting channel.And then it can be expected that the miniaturization of electronic component, it is productive carry it is high and low The realization of cost, therefore positive progress research and development related with printable conductive paste with all strength, and have a large amount of motion.

About conductive paste, thus it is ensured that for the viewpoint of high conductivity, the main silver used using silver-colored (Ag) as principal component Paste.However, under energization of the silver paste under high temperature, high humidity, easy tos produce silver atoms ionization and be introduced into ion in electric field and mobile It migrates (ion migration) (electrolysis).If generating Ion transfer on wiring circuit, there is the short circuit between causing circuit, match The anxiety of the reliability reduction of line circuit.

Therefore, in order to improve the reliability of electronic equipment or wiring, it is proposed that use the electroconductive paste of copper using silver is replaced Technology.Copper is not susceptible to Ion transfer, therefore the connection reliability of circuit can be improved.In addition, because its ion transport is low, therefore Can the difficult circuit pattern that electric signal is alternately transmitted in wiring closet for silver be realized by using copper paste.

However, usually copper powder is easy oxidation, if being exposed in the environment of high humility, it is easy because of moisture contained in environment Or oxygen etc. reaction and generate Cu oxide.Therefore, there is the influence because of oxide film thereon in the conductive film calcining of copper paste formed And the volume resistivity of conductive film totality the problems such as being easy to get higher.

It is such in order to solve the problems, such as, it is proposed that the skill of the copper powders during allotment is pasted to copper is manufactured using wet-type reduction method Art, but the rising of the volume resistivity for the electroconductive paste that actual conditions are circuit layout is not fully improved.

Circuit layout copper paste energization mechanism (mechanism) be because calcining when film volume change due to copper Powder is crimped each other, therefore electric conductivity is significantly by the interstitital texture of the resin in the state of oxidation of Copper Powder Surface, film It influences.

Since before, it is proposed that allocate catechol (catechol), resorcinol (resorcin) in copper paste, to benzene The such oxygen that there is the substance (hereinafter referred to as reducing agent) of reduction and prevent Copper Powder Surface of diphenol (hydroquinone) The technology (such as patent document 1) of change.In addition, it is proposed that the oxidation of Copper Powder Surface is prevented using the reduction of ascorbic acid Technology (such as patent document 2 and patent document 3).

Existing technical literature

Patent document

Patent document 1：Japanese Patent Laid-Open 8-73780 bulletins

Patent document 2：No. 2014/104032 bulletin of International Publication No.

Patent document 3：Japanese Patent Laid-Open 2015-049988 bulletins

Invention content

Problem to be solved by the invention

As described above, important for the conductive film that the oxidation of inhibition Copper Powder Surface is formed for using copper to paste.However, specially In method described in sharp 1~patent document of document 3, the reducing agent allocated is unable to fully inhibit the oxidation of copper.The present invention's It is designed to provide a kind of conductive composition, that is, is convenient for the calcining (following otherwise referred to as dry or hardening) under air When situation, the conductive film for showing good electric conductivity and humidity resistance can be also formed.

Technical means to solve problem

The inventors of the present invention people is concentrated on studies in order to solve described problem, as a result, it has been found that, it is important that inhibit copper Powder surface aoxidizes and keeps the contact between copper powder secured, so that complete the present invention.

That is, the present invention relates to a kind of conductive composition, it includes surface treatment copper powder (AB), adhesive resin (C) with And the dispersant (D) with acidic groups, wherein the surface treatment copper powder (AB) is to be attached with following lead on the surface of copper powder (A) Ascorbic acid represented by formula (1) or general formula (2) or derivatives thereof (B).

General formula (1)

[changing 5]

(in general formula (1), R1 and R2 separately indicate hydrogen atom or can have the acyl group of substituent group.)

General formula (2)

[changing 6]

(in general formula (2), R11 and R12 separately indicate hydrogen atom or can have the alkyl of substituent group.)

Moreover, it relates to which a kind of manufacturing method of conductive composition, makes described ascorbic acid or derivatives thereof (B) it is attached to the surface of copper powder (A), surface treatment copper powder (AB) is obtained, by the surface treatment copper powder (AB), adhesive resin (C) and the dispersant with acidic groups (D) mixes.

In turn, the present invention relates to a kind of conductive materials, have base material and conductive film, and the conductive film is the conduction The dried object or hardening thing of property composition.

The effect of invention

Through the invention, it is possible to provide a kind of conductive composition and its hardening thing, sandwich, the conductive composition are Just good electric conductivity is also showed that in the calcining under air, can be used to form circuit.

Description of the drawings

Fig. 1 is the particle surface to surface treatment copper powder (AB) used in embodiment 1 using scanning electron microscope The figure observed of state.

Fig. 2 is the grain to surface treatment copper powder (AB) used in embodiment 1 using energy dispersion-type X-ray analytical equipment The state in sublist face is observed, and the figure of Match of elemental composition is carried out to carbon and copper.

Specific implementation mode

[conductive composition]

The conductive composition of the present invention includes to utilize ascorbic acid or derivatives thereof (B) (below as described above Be simply referred as ascorbic acid derivates (B)) surface of copper powder (A) is handled made of surface treatment copper powder (AB), viscous Mixture resin (C) and dispersant (D) with acidic groups.

<It is surface-treated copper powder (AB)>

The surface treatment copper powder (AB) used in the present invention becomes the conductive compositions of conductive composition.It is surface-treated copper powder (AB) it is that ascorbic acid derivates (B) are attached in at least part on the surface copper powder (A).Derive by using ascorbic acid Object (B) is coating by at least part on the surface copper powder (A), and the ascorbic acid derivates as reducing substances can be made to be present in copper Near the surface powder (A), it as a result can make to be formed by Cu oxide when calcining conductive composition in an atmosphere efficiently also It is former and revert to copper, electric conductivity can be improved.

<Copper powder (A)>

The D50 average grain diameters of copper powder (A) are preferably in the range of 0.1 μm~30 μm, more preferably at 0.1 μm~10 μm In the range of.It is 0.1 μm or more by D50 average grain diameters, the mutual contact resistance of particle in conductive film can be further decreased, Improve electric conductivity.In addition, by D50 average grain diameters for 30 μm hereinafter, can be formed when progress screen painting makes conductive film Smoother conductive film.Furthermore D50 average grain diameters are to use the volumetric particle size calculated by laser diffraction granularity distribution measurement device The connotation of accumulative 50% granularity of distribution.

About the shape of copper powder (A), as long as can get required electric conductivity, shape is simultaneously not limited.Specifically, example The copper powder of shape as known in can be used spherical, thin slice (flake) shape, lobate, dendroid, plate, needle-shaped, rodlike, botryoidalis etc..

<Ascorbic acid derivates (B)>

Ascorbic acid or derivatives thereof used in the present invention (B) is represented by the following general formula (1) or general formula (2).It is right The power reducing source of Cu oxide is from enediol (enediol) structure in ascorbic acid derivates (B).It therefore, also can be with residual The form of the structure and the derivative for synthesizing ascorbic acid, it is appropriate to prepare solubility or polarity and use.

General formula (1)

[changing 7]

(in general formula (1), R1 and R2 separately indicate hydrogen atom or can have the acyl group of substituent group.)

The acyl group (- COR) of R1 and R2 in general formula (1) indicate that bond has the straight-chain, branch's chain state, list of carbon number 1~18 Cyclic annular or condensation polycyclic shape aliphatic carbonyl, or it is bonded the monocycle shape or condensation polycyclic shape aryl for having carbon number 6~10 Carbonyl.

Acyl group is specifically, can for example enumerate：Formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, Isovaleryl, pivaloyl group, lauroyl, myristoyl, palmityl, stearyl, cyclopentylcarbonyl, cyclohexyl Carbonyl, acryloyl group, methylacryloyl, crotonyl, methacrylyl, oleoyl, benzoyl, 1- naphthoyls, 2- Naphthoyl etc., but it is not limited to these groups.

The acyl group of R1 and R2 can be replaced the hydrogen atom in acyl group by substituent group respectively, thus also can further adjust dissolving Property or polarity.Herein, substituent group can enumerate hydroxyl, halogen atom etc., and but not limited thereto.

General formula (2)

[changing 8]

(in general formula (2), R11 and R12 separately indicate hydrogen atom or can have the alkyl of substituent group.)

General formula (2) is by making aldehydes or ketones form acetal with two hydroxyl reactions being present on the side chain of ascorbic acid The derivative of structure or ketal structure.

The alkyl of R11 and R12 in general formula (2) can enumerate straight-chain, branch's chain state, monocycle shape or the contracting of carbon number 1~18 Polycyclic alkyl is closed, specifically, can for example enumerate：Methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl Base, decyl, dodecyl, octadecyl, isopropyl, isobutyl group, isopentyl, sec-butyl, tertiary butyl, sec-amyl, tertiary pentyl, uncle Octyl, neopentyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, adamantyl, norborny and 4- decyl cyclohexyl etc., but It is not limited to these groups.

The alkyl of R11 and R12 can be replaced the hydrogen atom in alkyl by substituent group respectively, thus also can further be adjusted molten Solution property or polarity.Herein, substituent group can enumerate hydroxyl, halogen atom etc., but be not limited to these groups.

In turn, R11 and R12 also integrally can form ring structure.

In ascorbic acid derivates (B) represented by general formula (1) or general formula (2), so that it may most inexpensively obtain, and due to molten Xie Du is low and is difficult to from for the dissolving of the surface of copper powder (A) or the aspect being detached from, and the R1 and R2 preferably in general formula (1) are that hydrogen is former The ascorbic acid of son.In addition, ascorbic acid derivates (B) also can be to copper powder (A) and with two or more.

Used in the so-called present invention " ascorbic acid ", commonly known as ascorbic L-AA, i.e. is referred not only to (R) -3,4- dihydroxy -5- ((S) -1,2- dihydroxy ethyls) furans -2 (5H) -one also includes its optical isomeric compound (D bodies).Separately Outside, also include stereoisomers as these compounds arabo-ascorbic acid D bodies and L bodies.Even if for stereoisomers or Optical isomeric compound can also have enediol structure necessary to performance reducing power and show same reducing power.In turn, The DL bodies of mixture as these optical isomeric compounds also are used as " ascorbic acid " of the present invention.

The ascorbic acid derivates (B) of the present invention can illustrate such compound as shown below.Furthermore of the invention is anti-bad Hematic acid derivative (B) is not limited to these typical examples." * " in each chemical constitution indicates that X, Y or Z are bonded to the five of ascorbic acid The position at membered ring position.

[changing 9]

[changing 10]

[changing 11]

<It is surface-treated the manufacturing method of copper powder (AB)>

About surface treatment copper powder (AB), it is not limited to the following method, such as can use or deform by using dispersion and use Medium (media) makes copper powder (A) collide and obtain with ascorbic acid derivates (B).Dispersion use or deformation medium can be used with The spherical beads as material such as glass, steel (steel), zirconium oxide.

The contact procedure can be carried out using dry type, the either method of wet type.

That is, in the situation of dry type, such as by copper powder (A), ascorbic acid derivates (B) and disperse use or deformation medium It is put into container, after sealing, rotates or vibrate together with container, or to being stirred in container, thus make these objects Matter is collided, and copper powder (A) is attached to when making part or all for making ascorbic acid derivates (B) when copper powder (A) deformation Behind surface, dispersion or deformation are detached with medium, thus can get surface treatment copper powder (AB).

In addition, in the situation of wet type, copper powder (A), ascorbic acid derivates (B), liquid medium, dispersion are used or deformed It is put into container with medium, is rotated, vibrated, stirred as described above, after thus colliding these substances, utilized Nylon wire or stainless (steel) wire etc. will disperse or deformation is removed with medium, then removes liquid medium, is subject to drying, thus can obtain Copper powder (AB) must be surface-treated.

When making dispersion use or deformation medium and the dispersion steps of copper powder (A) collision described in implementation, usable ball mill, Dispersing method well known to ball mill, sieve shaker (shaker) etc..

Used liquid medium can enumerate alcohol system, ketone system, ester system, aromatic system, hydrocarbon when carrying out the situation of wet type dispersion The two or more of these media, can also be used in mixed way by the well known liquid medium of system etc., as long as at a temperature of implementing to disperse In liquid, then it is not particularly limited.

In such liquid medium, if using the relatively low poor solvent of the solubility of ascorbic acid derivates (B), it can The special surface for efficiently making ascorbic acid derivates (B) be attached to copper powder (A) with required amount, therefore it is preferred that.Ascorbic acid The poor solvent of derivative (B) can enumerate toluene, dimethylbenzene, hexane, octane, isopropanol, ethyl acetate and then these solvents Mixed solvent, but it is not limited to these solvents.

It is especially used using dispersion or the wet type of deformation medium and liquid medium disperses to be easy to utilize by easy operation Ascorbic acid derivates (B) are uniform and efficiently coating by the surface copper powder (A), in this connection preferably.In turn, described wet In formula dispersion, the big flake of the mutual contact area of particle or lobate coating copper powder (AB) are can get, as a result can express out Excellent initial stage electric conductivity, and then the electric conductivity is maintained, therefore it is preferred that.

Ascorbic acid derivates (B) preferably use the mass parts of 1 mass parts~30 relative to 100 mass parts of copper powder (A), And then preferably in the range of 5 mass parts~10 mass parts.By the way that ascorbic acid is set as 1 mass parts or more, it can inhibit and forge The oxidation of the copper of surface treatment copper powder (AB) when burning, and then improve the parent of surface treatment copper powder (AB) and adhesive resin (C) And property.In addition, by the way that ascorbic acid is set as 30 below mass part, surface treatment copper powder (AB) mutual cohesion can inhibit.

<Adhesive resin (C)>

Adhesive resin (C) is preferably in total 100 mass % of adhesive resin (C) and surface treatment copper powder (AB) Allocate the 5 mass % of mass %~40, more preferably 5 mass of mass %~25 %.By becoming 5 mass % or more, electric conductivity quilt The adhesion of film and base material further increases, and mechanical strength also improves.In addition, by become 40 mass % hereinafter, electric conductivity into One step improves.

Adhesive resin (C) can for example be enumerated：Acrylic resin, polybutadiene system resin, epoxide, oxa- ring Butane resin, piperazine polyamide, add-on type ester resin, condensed type ester resin, amino resins, polylactic resin, oxazolines Resin, benzoxazine colophony, vinylite, diolefin resins, terpene resin, Petropols, cellulose-based resin, polyester tree Fat, carbamate modification polyester resin, epoxy modification polyester resin, (methyl) acrylic resin, styrene resin, benzene second Alkene-(methyl) acrylic resin, styrene-butadiene resins, epoxy resin, modification epoxy resin, phenoxy resin, chloroethene Alkene-vinyl acetate copolymer, butyral resin, acetal resin, phenol resin, polycarbonate resin, polyether resin, polyurethane Ester resin, polyurethanes carbamide resin, polyamide, polyimide resin, polyamide-imide resin, alkyd resin, Vistanex, fluororesin, ketone resin, benzoguanamine resin, melmac, carbamide resin, silicone resin, nitrocellulose Element, cellulose acetate-butyrate (Cellulose Acetate Butyrate, CAB) resin, cellulose-acetate propionate Resin well known to (Cellulose Acetate Propionate, CAP) resin, rosin, rosin ester and maleic acid resin etc., can Physical property required by conductive composition according to the present invention, conductive film and conductive material and suitably select.In addition, adhesive Resin (C) can be used alone or be used in combination two or more.

The polyester resin be preferably with hydroxyl and carboxyl at least any one.Polyester resin can utilize polyacid with it is more Synthetic method well known to the reaction of first alcohol etc. or polybasic ester and the ester exchange reaction of polyalcohol etc. etc. and synthesize.In addition, to polyester Well known method can be used in the method that resin assigns carboxyl, such as can enumerate：After polymerizeing to polyester resin, at 180 DEG C~230 DEG C Under so that the cyclic esters such as 6-caprolactone is carried out after addition (open loop addition) and the method that forms block (block)；Or the inclined benzene of addition three The method etc. of the acid anhydrides such as formic anhydride, phthalic anhydride.In addition, polyester resin is preferably saturated polyester.

The polyacid is such as preferably aromatic dicarboxylic acid, straight-chain aliphatic dicarboxylic acids, annular aliphatic dicarboxylic acids And carboxylic acid etc. more than trifunctional.Furthermore polyacid includes the compound containing anhydride group.Polyacid can be used alone or be used in combination two Kind or more.

Aromatic dicarboxylic acid is not limited to these compounds such as can enumerate terephthalic acid (TPA) and M-phthalic acid. In addition, straight-chain aliphatic dicarboxylic acids be such as can enumerate adipic acid, decanedioic acid and azelaic acid, but it is not limited to the compound. In addition, annular aliphatic dicarboxylic acids can for example enumerate Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, dicarboxyl hydrogenated bisphenol A, dimeric dibasic acid, 4- methyl Hexahydrophthalic anhydride and 3- methylhexahydrophthalic anhydrides etc., but it is not limited to these compounds.In addition, trifunctional with On carboxylic acid can enumerate trimellitic anhydride and pyromellitic acid anhydride etc., but do not limit these compounds.Other carboxylic acids also may be used The dicarboxylic acids etc. containing metal organic sulfonate such as the unsaturated dicarboxylics such as fumaric acid, 5- sulfo isophthalate sodium salts is enumerated, but unlimited Due to these compounds.

The polyalcohol be preferably glycol and tool there are three above hydroxyl compound.Glycol can for example enumerate second two Alcohol, propylene glycol and 1,4-butanediol and neopentyl glycol etc., but it is not limited to these compounds.There are three above hydroxyls for tool Compound can enumerate trimethylolpropane, glycerine and pentaerythrite etc., but be not limited to these compounds.Polyalcohol can be independent Using or be used in combination two or more.

The polyurethane resin be make polyalcohol, diisocyanate and chain elongation agent diol compound react and At end have hydroxyl compound.Polyurethane resin can be used chain elongation agent by molecule chain elongation.Chain elongation Agent is preferably generally glycol etc..Polyurethane resin can be synthesized using well known synthetic method.

Polyalcohol for synthesizing polyurethane resin is preferably polyether polyol, polyester polyol, makrolon Polyalcohol and polybutadiene diol.Polyalcohol can be used alone or be used in combination two or more.

Polyether polyol is the polymer of ethylene oxide, propylene oxide and tetrahydrofuran etc. and the copolymerization of these compounds Object.

Polyester polyol is the polyalcohol and polybasic ester illustrated in the polyester resin.

Polycarbonate polyol is preferably compound made of 1) making glycol or bis-phenol and carbonate reaction and 2) makes glycol Or bis-phenol reacted in the presence of base with phosgene (phosgene) made of compound etc..Carbonic ester can for example enumerate carbonic acid diformazan Ester, diethyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate etc., but it is not limited to these compounds.

Diisocyanate is preferably aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate etc.. Diisocyanate can be used alone or be used in combination two or more.

The polyurethanes carbamide resin has isocyanide to make polyalcohol and di-isocyanate reaction synthesize in end The carbamate prepolymer of perester radical, and then compound made of making it be reacted with polyamines.In addition, for polyurethanes For carbamide resin, reaction stopping agent can optionally be made to react to adjust molecular weight.Polyalcohol and diisocyanate are preferably Use the compound illustrated in the polyurethane resin.Polyamines is preferably diamines.It is preferably dialkyl group to react stopping agent Amine, single methanol etc..Polyurethanes carbamide resin can be synthesized using well known synthetic method.

Polyurethane resin and polyurethanes carbamide resin preferably also have carboxyl other than hydroxyl.Specifically For, synthetic method can be carried out using a part for glycol is substituted for carboxylic glycol in synthesis and obtained.Institute It is preferably dihydromethyl propionic acid and dimethylolpropionic acid etc. to state glycol.

When conductive paste includes the situation of polyurethane resin or polyurethanes carbamide resin, it is formed by and leads The hardness of electrical envelope further increases.

Solvent can be used when synthesizing polyurethane resin or polyurethanes carbamide resin.Specifically, it is preferable that For ester series solvent, ketone series solvent, glycol ether series solvent, fatty family solvent, aromatic system solvent and carbonate-based solvent etc..It is molten Agent can be used alone or be used in combination two or more.

Ester series solvent can for example enumerate ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, pentyl acetate, Ethyl lactate and dimethyl carbonate etc., but it is not limited to these compounds.

Ketone series solvent can for example enumerate acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, diisobutyl ketone, Diacetone alcohol, isophorone and cyclohexanone etc., but it is not limited to these compounds.

Glycol ether series solvent can for example be enumerated：Ethylene glycol monoethyl ether, ethyleneglycol monopropylether and ethylene glycol monobutyl ether etc. are single The acetic acid esters of ether and these compounds；Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, diethyl two The acetic acid esters etc. of alcohol monobutyl ether, propylene glycol monomethyl ether and dihydroxypropane single-ether etc. and these compounds, but it is not limited to these Compound.

Fatty family solvent is not limited such as can enumerate n-hexane, hexamethylene, hexahydrotoluene, hexahydrotoluene In these compounds.

Aromatic system solvent can enumerate toluene, dimethylbenzene etc., but be not limited to these compounds.

Carbonate-based solvent can be enumerated：The linear carbonates such as diethyl carbonate, ethylmethyl carbonate, ethylene carbonate, Cyclic carbonates such as propylene carbonate etc., but it is not limited to these compounds.

The epoxy resin is the compound with epoxy group and hydroxyl, and well known compound can be used.Epoxy resin is excellent It is selected as making the aromatic diol representated by bisphenol-A and Bisphenol F to react the polyglycidyl ether of gained with epichlorohydrin.Epoxy resin Preferably used as the so-called phenoxy resin of macromolecule epoxy resin.These resins can be used alone or be used in combination two or more.

Hereinafter, the selected concrete example as the adhesive resin (C) used in conductive composition of the invention, to leading Electrically two of paste and conductive adhesive or conductive sheet are described.Furthermore purposes of the invention is not limited to these Purposes.

<Situation for conductive paste>

First, when the conductive composition of the present invention to be used for the situation to make the conductive paste of wiring circuit, Just to the viewpoint of the mechanical strength of film necessary to the adhesion of base material, dissolubility in a solvent, conductive composition and Speech, adhesive resin (C) are preferably selected from by phenoxy resin, polyester resin, polyurethane resin, polyurethanes urea In the group that resin and epoxy resin are formed.In addition, these resins in the following areas for it is also preferred that：With with acidic groups Dispersant (D) combination situation when, surface treatment copper powder (AB) dispersibility it is excellent.These adhesive resins can be used alone Or it is used in combination two or more.

The number average molecular weight (hereinafter referred to as Mn) of the adhesive resin (C) of the situation is preferably 10,000~50, 000, more preferably 20,000~40,000.Becoming 10,000 or more by Mn, the environmental reliability of conductive composition improves, Especially humidity resistance further increases.Furthermore Mn is to utilize gel permeation chromatograph (Gel Permeation Chromatography, GPC) measured polystyrene conversion numerical value.In addition, the environmental reliability of so-called wiring circuit, Even if referring to being placed in 85 DEG C, in the environment of humidity 85%, the oxidation institute by conductive composition or conductive film itself is also not present The deterioration of cause, conductive film are difficult to deteriorate to the adhesion of base material (such as tin indium oxide (Indium Tin Oxide, ITO) film).

The glass transition temperature (hereinafter referred to as Tg) of the adhesive resin (C) of the situation is preferably 5 DEG C~100 DEG C, more excellent It is selected as 10 DEG C~95 DEG C.If Tg becomes 5 DEG C or more, the humidity resistance of wiring circuit further increases.In addition, if Tg becomes 100 DEG C hereinafter, then the adhesion of wiring circuit and base material further increases.Furthermore Tg is to utilize differential scanning calorimetry The numerical value that (Differential Scanning Calorimeter, DSC) is measured.

If the adhesive resin of the situation meets the Mn and the Tg simultaneously, the reliability of wiring circuit is further It improves, therefore most preferably.

<Situation for conductive adhesive or conductive sheet>

Then, when the conductive composition of the present invention to be used for the situation of conductive adhesive or conductive sheet etc., For cementability, pliability, the viewpoint of painting processability, adhesive resin (C) is particularly preferably polyurethane resin, gathers Carbamate carbamide resin, add-on type ester resin, epoxy resin, phenoxy resin, polyimide resin, polyamide, piperazine Polyamide, polyamide-imide resin.In addition, these resins in the following areas for it is also preferred that：With with acidic groups Dispersant (D) combination situation when, surface treatment copper powder (AB) dispersibility it is excellent.These adhesive resins can be used alone Or it is used in combination two or more.

The adhesive resin of the situation and then preferably thermosetting, specifically, it is preferable that for have in the structure at For the carboxyl of the starting point of sclerous reaction.In turn, these adhesive resins (C) can be also used in combination with curing agent.

The acid value of the adhesive resin (C) of the situation is not particularly limited, preferably 3mgKOH/g~100mgKOH/g, More preferably 3mgKOH/g~70mgKOH/g.Particularly preferably 3mgKOH/g~40mgKOH/g.By by adhesive resin (C) Acid value be set as the range of 3mgKOH/g~100mgKOH/g, flexible and environmental reliability further increases.

The Tg of the adhesive resin (C) of the situation is preferably -30 DEG C~30 DEG C, more preferably -20 DEG C~20 DEG C.Pass through Tg is set as to -30 DEG C~30 DEG C of range, flexible and adhesive strength further increases.

The weight average molecular weight (hereinafter referred to as Mw) of the adhesive resin (C) of the situation is preferably 20,000~100, 000.By the way that Mw is set as 20,000~100,000, flexible and adhesive strength further increases.

With the curing agent of thermosetting adhesive resin (C) be with it is multiple can in adhesive resin (C) The material of the functional group of carboxyl reaction.Such as epoxide, isocyanate compound, amine compounds, aziridine can be enumerated Close compound well known to object, organo-metallic compound, the compound containing anhydride group, phenolic compounds etc..Preferably epoxide Or aziridine cpd.Curing agent can be used alone or be used in combination two or more.

<Dispersant (D) with acidic groups>

In the present invention, the dispersant (D) with acidic groups is surface treatment copper powder (AB) dispersion in order to be difficult to disperse It is used in conductive composition.In addition, if conductive composition includes dispersant, adhesive resin and surface treatment copper The particulate of powder (AB) is easy mixing and dispersibility improves, therefore the viscosity pasted reduces, the surface treatment in printing in coated film The particulate of copper powder (AB) is easy more closely to arrange, and interparticle contact can be made to increase.Such dispersant is preferably resin type Dispersant.

Resin type dispersant is usually with the compatibility position for being adsorbed in the particle as dispersed objects and to adhesive The dispersant of the polymer (resin) at the high position of resin compatibility.The compatibility position can enumerate carboxyl, phosphate, sulfonic acid Acidic groups such as base, hydroxyl, maleic etc..In the present invention, it is necessary to have acidic groups is as the parent to surface treatment copper powder (AB) With property position.If being adsorbed in surface treatment copper powder (AB) securely, even if also interfering the conduction between copper particle logical in calcining Road, therefore the acidic groups of the adsorption capacity preferably with appropriateness.In addition, in acidic groups, preferably also with the absorption of copper or desorption Good phosphate.

In the present invention, in the dispersant (D) with acidic groups, commercially available product can also be used in resin type dispersant.Commercially available product example It can such as enumerate：Di Sipabike (DISPER BYK) -102, the Di Sipabike of Bi Ke chemistry (BYK Chemie) company manufacture (DISPERBYK) -110, Di Sipabike (DISPERBYK) -111, Di Sipabike (DISPERBYK) -118, Di Sipabi Gram (DISPER BYK) -170, Di Sipabike (DISPER BYK) -171, Di Sipabike (DISPERBYK) -174, Di Si Pa Bike (DISPERBYK) -2096, Bi Ke (BYK)-P104, Bi Ke (BYK)-P104S, Bi Ke (BYK)-P105, Bi Ke (BYK)-220S；Fu Luolan (Flowlen) G-700, Fu Luolan (Flowlen) of chemistry limited liability company of common prosperity society manufacture GW-1500, Fu Luolan (Flowlen) G-100SF, Fu Luolan (Flowlen) AF-1000, Fu Luolan (Flowlen) AF-1005； The rope of Lu Borun (LUBRIZOL) company manufacture exerts Paasche (SOLSPERSE) -3000, rope exerts Paasche (SOLSPERSE) -21000, Rope exerts Paasche (SOLSPERSE) -36000, rope exerts Paasche (SOLSPERSE) -36600, rope exerts Paasche (SOLSPERSE) - 41000, rope exerts Paasche (SOLSPERSE) -41090, rope exerts Paasche (SOLSPERSE) -43000, rope exerts Paasche (SOLSPERSE) -44000, rope exerts Paasche (SOLSPERSE) -46000, rope exerts Paasche (SOLSPERSE) -55000, Suo Nupu Lars (SOLPLUS)-D520, the Lars Suo Nupu (SOLPLUS)-D540, the Lars Suo Nupu (SOLPLUS)-L400 etc..

Dispersant (D) used in the present invention with acidic groups is preferably also with amino.Amino can be level-one, two Grade, three-level it is any.Amino preferably neutralizes the acidic groups.

Though detailed reason is still unknown, the suitable of the resin type dispersant that there is the substance of amino to neutralize acidic groups is utilized Reason is contemplated that as follows.In conductive composition, the substance with amino is coordinated in the Vitamin C in surface treatment copper powder (AB) Acid, if being heated in calcining, the substance with amino makes the variation of the ascorbic acid in surface treatment copper powder (AB) be active form Molecular skeleton, promote to be formed by the redox reaction of Cu oxide and ascorbic acid in calcining.And then investigate and arrive, because Heating and ascorbic acid is consumed, the substance with amino is coordinated in the copper surface of exposing, thus can inhibit copper when calcining Oxidation and the oxidation of the copper under hygrothermal environment.

If considering complexing strength, the substance with amido is in turn preferably in molecular end with the alkanol for keeping hydroxyl Amine skeleton.

In resin type dispersant, the position high to adhesive resin compatibility can for example be enumerated：Polyurethanes and poly- The polycarboxylates polyamide such as acrylate；Polycarboxylic acids, polycarboxylic acids ammonium salt, polycarboxylic acids alkylamine salt, gathers polycarboxylic acids (part) amine salt The polycarboxylate of siloxanes, long-chain polyaminoamide phosphate and hydroxyl；By poly- (low-grade alkylidene imines) and with free Amide and its salt synthesized by the reaction of the polyester of carboxyl etc..

In addition, other positions high to adhesive resin compatibility can be enumerated：Polyester, polyethers, polyester ether, polyurethane The polyphosphoric acid (salt) of ester etc.；Polyphosphoric acid, polyphosphoric acid (part) amine salt, polyphosphoric acid ammonium salt, polyphosphoric acid alkylamine salt etc..

In addition, other positions high to adhesive resin compatibility can be enumerated：(methyl) acrylic-styrene copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone Ketone, vinyl chloride vinyl acetate copolymer, Polyester, modification polyacrylate system, ethylene oxide/propylene oxide combine additively Object and cellulose derivatives resin etc..

In the present invention, in the dispersant (D) with acidic groups, also the resin type dispersant with amino can also be used commercially available Product.Commercially available product can for example be enumerated：An Titela (ANTI-TERRA)-U of Bi Ke chemistry (BYK Chemie) company manufacture, peace carry Te La (ANTI-TERRA)-U100, An Titela (ANTI-TERRA) -204, Di Sipabike (DISPERBYK) -106, Di Si Pa Bike (DISPER BYK) -130, Di Sipabike (DISPER BYK) -140, Di Sipabike (DISPERBYK) -142, Di Sipabike (DISPERBYK) -145, Di Sipabike (DISPERBYK) -180, Bi Ke (BYK) -9076；Common prosperity society chemistry Fu Luolan (Flowlen) G-820XF of limited liability company's manufacture；The rope of Lu Borun (LUBRIZOL) company manufacture exerts Paasche (SOLSPERSE) -26000, rope exerts Paasche (SOLSPERSE) -53095, the Lars Suo Nupu (SOLPLUS)-D530 etc..

The conductive composition of the present invention preferably contains 0.1 matter relative to surface treatment copper powder (AB) 100 mass parts Measure the dispersant (D) with acidic groups of the mass parts of part~10, the mass parts of more preferably 0.6 mass parts~1.By containing 0.1 The dispersibility of dispersants (D) more than mass parts, surface treatment copper powder (AB) further increases.In addition, by by dispersant (D) It is set as 10 below mass part, the electric conductivity of conductive cell envelope further increases.

<Copper precursors (Y)>

The conductive composition of the present invention can also contain copper precursors.So-called copper precursors, to be changing into the object of copper in calcining Matter.

Copper precursors (Y) are preferably to allocate 0.1 in total 100 mass % of copper precursors (Y) and surface treatment copper powder (AB) The mass % of quality %~50, more preferably 1 mass of mass %~15 %.By being set as 0.1 mass % or more, and will surface treatment Copper powder (AB) is engaged with each other, and electric conductivity improves due to conductive path becomes stronger contact reinforcing effect.In addition, by being set as 50 mass % are hereinafter, and give full play to the resistance to oxidation effect for being surface-treated copper powder (AB).

In the present invention, copper precursors (Y) can for example be enumerated：Copper acetate, trifluoroacetic acid copper, propionic acid copper, copper butyrate, isobutyric acid Copper, 2-Methyl Butyric Acid copper, 2 Ethylbutanoic acid copper, valeric acid copper, isovaleric acid copper, pivalic acid copper, caproic acid copper, enanthic acid copper, cupric octoate, 2- The mantoquita of copper ethylhexanoate, n-nonanoic acid copper etc. and fat formula carboxylic acid, the copper with dicarboxylic acids such as malonic acid copper, succinic acid copper, maleic acid copper Salt, the mantoquita of copper benzoate, Cupric salicylate etc. and aromatic carboxylic acid, copper formate, hydroxyacetic acid copper, glyoxalic acid copper, copper lactate, grass The mantoquita with the carboxylic acid with reducing power such as sour copper, cupric tartrate, malic acid copper, copper citrate, copper nitrate, copper cyanider and acetyl Pyruvic acid copper etc..In these compounds, the high copper formate of copper containing ratio preferably in ingredient.

When the conductive composition of the present invention contains the situation of copper precursors (Y), it also can also contain the copper to copper precursors Reaction promoter.The so-called copper reaction promoter to copper precursors, it is more than one with to copper ion to contain in the molecule Or the compound of the functional group of the coordination ability of mantoquita, and to interact by being mixed with copper precursors (Y), make copper precursors (Y) material that decomposition temperature, i.e. copper temperature reduces.It is mainly with the functional group to copper ion or the coordination ability of mantoquita With the heteroatomic functional group such as oxygen atom, nitrogen-atoms, sulphur atom, more specifically, such as mercapto, amino, hydrazine can be enumerated Base, amide groups, itrile group, hydroxyl, hydroxycarbonyl group etc..In addition, copper reaction promoter, which can be low molecular compound, is alternatively high score Sub- compound.

The structure of copper reaction promoter is not particularly limited, big with regard to the reduction amplitude of the decomposition temperature of copper precursors, can be incited somebody to action For the aspect that the calcination temperature of conductive composition inhibits low, it is preferably selected from compound with amino, with mercaptan In the compound of base, and then maximum in the reduction amplitude of decomposition temperature, foreign odor also for few aspect, most preferably has amino Compound.

Copper reaction promoter with amino can enumerate aliphatic amine, cyclic amine, aromatic amine, can more specifically enumerate： Ethamine, n-propylamine, isopropylamine, n-butylamine, isobutyl amine, tert-butylamine, n-amylamine, n-hexylamine, cyclohexylamine, n-octyl amine, 2- ethyl hexyls Amine, dodecyl amine, n-hexadecyl amine, oleyl amine, stearylamine, ethanol amine, benzylamine, N- methyl n-propylamine, methyl isopropylamine, Methyl tert-butyl amine, methyl tert-butylamine, methyl n-hexylamine, methyl cyclohexylamine, methyl n-octyl amine, methyl -2 ethyl hexylamine, methyl are just Lauryl amine, methyl n-tridecane base amine, methyl n-hexadecyl amine, methyl stearylamine, diethylamine, dibutyl amine, dioctylamine, Two-lauryl amines, distearyl amine, diethanol amine, triethylamine, diethyl triethylamine, tri-n-butylamine, trioctylamine, three-dodecyls Amine, three stearylamines, triethanolamine, methylbenzylamine, aniline, n,N-Dimethylaniline, para-totuidine, methylphenylamine, 4- butyl Aniline, pyrrolidines, pyrroles, piperidines, pyridine, hexamethylene imine, pyrazoles, imidazoles, piperazine, N methyl piperazine, n-ethylpiperazine, 1,8- diazabicyclo (5,4,0), 11-7- alkene (1,8-diazabicyclo (5,4,0) undec-7-ene, DBU) etc., but not It is defined in these compounds.

<Electroconductive particle, electric conductivity composite microparticle>

The conductive composition of the present invention can also contain electroconductive particle.Electroconductive particle can for example enumerate silver, gold, platinum, Copper, nickel, manganese, tin, indium etc..

The conductive composition of the present invention can also contain conductive composite microparticle.Electric conductivity composite microparticle is with general The conductive particle of the coating coating in surface of nucleome.Herein, nucleome is cheap and high electric conductivity copper, and coating is to lead Resistance value electrically high and caused by acid value deteriorates few silver.Silver is for example alternatively and gold, platinum, silver, copper, nickel, manganese, tin and indium Deng alloy.

As long as the shape of electroconductive particle and electric conductivity composite microparticle can get required electric conductivity, shape has no It limits.Specifically, for example preferably spherical, laminar, lobate, dendroid, plate, needle-shaped, rodlike, botryoidalis.In addition, These electroconductive particles of different shapes or electric conductivity composite microparticle can be mixed two kinds.Electroconductive particle and electric conductivity are compound Particulate can be used alone or be used in combination two or more.

<Solvent>

The conductive composition of the present invention can also contain solvent.By containing solvent, the dispersion of surface treatment copper powder (AB) Become and be easy, is easily tailored as the viscosity suitable for printing.Solvent can be according to the dissolubility of used resin or printing process etc. Type and select.Solvent can be used alone or be used in combination two or more.

Specifically, it is preferable that molten for ester series solvent, ketone series solvent, glycol ether series solvent, fatty family solvent, aromatic system Agent and alcohol series solvent etc..

Ester series solvent can similarly can exemplified as synthesis polyurethane resin or when polyurethanes carbamide resin The solvent used and the solvent illustrated.And then it can also illustrate the cyclic annular ester series solvent such as 6-caprolactone and gamma-butyrolacton.

Ketone series solvent, glycol ether series solvent, fatty family solvent can be similarly exemplified as synthesis polyurethanes trees Workable solvent when fat or polyurethanes carbamide resin and the solvent illustrated.

Aromatic system solvent is not limited to these solvents such as can enumerate toluene, dimethylbenzene, tetrahydronaphthalene.

Alcohol series solvent can for example be enumerated：Methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, amylalcohol, Hexanol, enanthol, octanol, cyclohexanol, benzylalcohol, terpinol etc., but it is not limited to these solvents.

The amount of solvent is not particularly limited, relative to surface treatment copper powder (AB), adhesive resin (C) and with acidity 100 mass parts of gross mass of the dispersant (D) of base, mass parts of preferably 5 mass parts~400 or so, and then preferably 5 mass parts ~300 mass parts or so.By the amount of solvent in the range, aftermentioned printing or coating method can be suitably coped with.

<Other additives>

The conductive composition of the present invention, which optionally contains, changes the curing agent, reducing agent, rub resistance of adhesive resin Kind agent, infrared absorbent, ultra-violet absorber, aromatic, curing agent, antioxidant, organic pigment, inorganic pigment, defoaming Agent, plasticiser, fire retardant and moisturizer etc..

<The preparation method of conductive composition>

The conductive composition of the present invention can be by being allocated and being utilized raw material explained hereinbefore with set ratio Blender is mixed and is prepared.Planetary-type mixer (planetary mixer) and disperser can be used in blender (disperser) device well known to such as.In addition, by being disperseed other than blender, it can be by surface treatment copper powder (AB) More imperceptibly disperse.Dispersion machine can enumerate ball mill, ball mill and three-roll mill etc..

[conductive material]

The conductive composition of the present invention can be used and obtain conductive material.That is, by printing on substrates or coating The conductive composition of the present invention, and be dried or calcine, it can get and have base material and the hardening as conductive composition The conductive material of the conductive film of object.

The printing or coating are for example in addition to screen painting, flexographic printing, hectographic printing, intaglio printing, intaglio plate graph Other than brush, plate gravure coating method, engagement coating (kiss coat) mode, die coating (die coat) mode, lip can be used to apply Cloth (lip coat) mode, comma coating (comma coat) mode, blade (blade) mode, roller coating (roll coat) side Formula, blade coating (knife coat) mode, spraying coating (spray coat) mode, rod coating (bar coat) mode, spin coating (spin Coat) coating method well known to mode, dip-coating (dip coat) mode etc..

Additionally, it is preferred that be dried or calcining step by heat after printing.About dry or calcining step, can arrange It lifts dry well known to hot-air oven, infrared-ray oven and microwave oven and the compound baking oven that these baking ovens are combined etc. Or calciner plant.

In turn, when carrying out the calcining caused by heat, so-called light calcining can also be used.Light is calcined as coated film to be had Light absorption wavelength within the scope of light moment of wavelength be irradiated in coated film, the coated film of light is heated or is occurred because of radiation Photolysis reactions, the method for calcining coated film in a short time.The type of the light irradiated is not particularly limited, such as can be enumerated Mercury vapor lamp, metal halide lamp, chemical lamp, xenon lamp, carbon arc lamp, laser light etc..With the common heat using hot-air oven etc. Calcining is compared, and light calcining can calcine in a short time, therefore can inhibit the oxidation of copper powder, can inhibit caused by heating for a long time Base material deteriorates, therefore it is preferred that.If in addition, not having optical absorption band to irradiation light, heat labile base material can also be used.In addition, Using laser light as when the situation of irradiation light, by making its irradiated area change, any part in coated film can be made to show Electric conductivity.

In addition, the oxidation of copper powder when in order to inhibit to calcine in an atmosphere, conductive composition preferably printed and added After drying, is pressurizeed and destroy the gap between surface treatment copper powder (AB), reduced in the conductive film before calcining It is calcined after air, or reduces the air in the conductive film of calcining midway when pressurization and be carried out at the same time calcining.In addition, plus Environment when pressure can be that atmospheric pressure environment is alternatively reduced pressure atmosphere.

When the situation calcined after the pressurizing, other than using the general thermmohardening of hot-air oven etc., can also it adopt It is calcined with light described above.When the situation calcined while when pressurization, method is not particularly limited, such as can be enumerated and made With the pressurization of heated roller, hot pressing etc., wherein preferably utilize the hot pressing that can more uniformly heat with pressurization.

The processing conditions of hot pressing is not particularly limited, usually in 120 DEG C~190 DEG C or so of temperature, pressure 1MPa~3MPa It is carried out under conditions of left and right, 1 minute~60 minutes or so time.In addition, sometimes also after heating crimps at 120 DEG C~190 DEG C 10 minutes~90 minutes thermmohardenings of lower progress.

Base material has variously-shaped, is not particularly limited, preferably sheet substrate.Sheet substrate is not particularly limited, such as It can enumerate：Polyimide film, polyamidoimide film, polyphenylene sulfide film, it is poly- to benzene-paraphenylene terephthalamide's imines film, polyethers nitrile film, Poly (ether sulfone) film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, poly- carbonic acid Ester film, polychloroethylene film and polypropylene sorrel etc..It is formed with tin indium oxide (Indium in addition, can also enumerate on these films Tin Oxide, ITO) (indium oxide for mixing tin) layer ito film and be formed with the ito glass of ITO layer on a glass.In addition, Sheet substrate can also enumerate the ITO ceramics that ITO layer is formed on ceramic wafer.Furthermore ITO layer need not be formed in the whole of film or plate On a face, can also it be formed locally.For sheet substrate when carrying out the situation of reflow step, preferably polyphenylene sulfide and polyamides are sub- Amine, in the situation without reflow step, preferably polyethylene terephthalate.Base material other than sheet can be enumerated in glass Containing the substrate etc. for being soaked with epoxy resin in glass fiber.

The thickness of sheet substrate is not particularly limited, and is 50 μm~350 μm or so, more preferably 100 μm~250 μm.Profit With the thickness of the range, mechanical property, shape stability, dimensional stability and the operability (handling) of sheet substrate etc. It is easy to become appropriate.

The thickness of conductive film is not particularly limited, and is drawn on the way in circuit, it is often preferred that and 3 μm~30 μm, more preferably It is 4 μm~10 μm.Become 3 μm~30 μm by thickness, is further increased with the adhesion of sheet substrate.In addition, with sheet Conductive layer etc. form using conductive film use on the way, preferably 1 μm~100 μm, more preferably 3 μm~50 μm.Pass through thickness Degree is easy to have both other physical property such as electric conductivity and bending resistance in the range of 1 μm~100 μm.

Also other materials can be laminated on conductive film.

Mobile phone, intelligence can be for example suitably used for by being formed by wiring circuit using the conductive composition of the present invention Mobile phone, tablet terminal, notes type PC (Personal Computer, PC), auto navigation (car navigation) etc. Touch-screen display (touch panel display).Though in addition, also can unlimitedly be used for displayless but have wiring The electronic equipment etc. of circuit, such as digital camera (digital camera), video recorder (video camera), compression optical disc (Compact Disk, CD)/digital audio-video optical disc (Digital Video Disc, DVD) player etc..In turn, it can also be used to Utilize radio frequency identification (the Radio Frequency that wiring circuit is formed by using conductive composition Identification, RFID) antenna circuit, wireless (wireless) for electric installation receiving coil and transmission line Circle.

Even if in addition, the conductive composition of the present invention can also provide one kind under air calcining has good electric conductivity And keep base material adhesion, heat-resisting moisture resistance environmental reliability conductive sheet.The type of conductive sheet can be suitably It enumerates Anisotropically conductive sheet material, destatic sheet material, earthy sheet material, thin film circuit (membrane circuit) use, electric conductivity The joining sheet material, heat conductivity sheet material, wire jumper circuit (iumper circuit) are with conductive sheet, electromagnetic wave shielding conductive sheet Material etc..

[embodiment]

Hereinafter, enumerate embodiment, the present invention is described in detail in comparative example, but the present invention be not only defined in it is below Embodiment.Furthermore " part " refers to " mass parts ", and " % " refers to " quality % ".

[copper powder (A)]

A1：(D50 grain sizes are 10 μm to branch copper powder, Bu Ete (Brunauer-Emmett-Tellern, BET) specific surface area For 0.3m²/g)

A2：(D50 grain sizes are 6.5 μm to spherical copper powder, BET specific surface area 0.13m²/g)

A3：(D50 grain sizes are 1.1 μm to spherical copper powder, BET specific surface area 0.64m²/g)

<The D50 particle size determinations of copper powder>

Volume is measured using laser diffraction granularity distribution measurement device " SALD-3000 " (manufacture of company of Shimadzu Seisakusho Ltd.) The cumulative particle sizes (D50) of size distribution.

<BET specific surface area>

It will be according to using flow-type specific area measuring device " not Lip river institute (Flowsoap) II " (Shimadzu Seisakusho Ltd.'s corporation Make) surface area that is measured is defined as specific surface area using the value that calculating formula below is calculated and recorded.

Specific surface area (m²/ g)=surface area (m²)/powder quality (g)

[ascorbic acid or derivatives thereof (B)]

B1：L-AA

B2：Ascorbyl palmitate

B3：(+) -5,6-O- isopropylidenes-L-AA

[surface treatment copper powder (AB)]

26.87g copper powder A1,1.34g ascorbic acid derivates B1 is added in vial：L-AA, 33g toluene and The bead of the 1mm of 25g, acutely concussion mixing.Thereafter, it is filtered using nylon wire, thus removes glass from stirring thing Pearl, and then be separated by filtration toluene from stirring thing by being filtered under diminished pressure, obtain solid content.The further vacuum of solid content is done It is dry, thus to obtain surface treatment copper powder (AB).

Using scanning electron microscope S-4300 (Hitachi (HITACHI) manufacture) with accelerating potential 5kV, 10000 times it is right The state of the particle surface of the surface treatment copper powder (AB) of gained is observed (Fig. 1), and then uses energy dispersion-type X-ray point Analysis apparatus EX-370 (rising abruptly manufactured by the making of field) carries out Match of elemental composition (Fig. 2) to carbon and copper.The distribution of carbon is equivalent to ascorbic acid Derivative B1, therefore according to the observation, it is to be attached with the surface of ascorbic acid derivates B1 on the surface of copper powder A1 to confirm it Handle copper powder (AB).

In addition, the surface treatment copper powder (AB) is warming up to 550 DEG C under a nitrogen, weight of the research from organic matter subtracts Few, the substantially total amount for as a result confirming added ascorbic acid derivates B1 is integrated with copper powder A1.

[copper precursors (Y)]

Copper formate tetrahydrate is dried in vacuo after obtaining anhydrous copper formate at 40 DEG C, mortar is utilized to crush 5 minutes.

[adhesive resin (C)]

<Adhesive resin C1>

By 40 parts of JERl256, (bisphenol A type epoxy resin, Mn=25,000, Tg is 95 DEG C, epoxide equivalent 7,500, hydroxyl Base price is 190, Mitsubishi Chemical Ind's manufacture) it is dissolved in 30 parts of isophorones and 30 parts of gamma-butyrolactons, obtain nonvolatile component For the solution of 40% adhesive resin C.

<Adhesive resin C2>

In the reaction vessel for having blender, thermometer, reflux condenser, dropper, nitrogen ingress pipe, addition 414 parts by adipic acid and terephthalic acid (TPA) and 3- methyl-1s, glycol, the 8 parts of dihydroxymethyls of the Mn=1006 obtained by 5- pentanediols Butyric acid, 145 parts of isophorone diisocyanate and 40 parts of toluene react 3 hours at 90 DEG C in a nitrogen environment.Add wherein Add 300 parts of toluene, obtains the solution for the carbamate prepolymer that there is isocyanate group in end.Then, in 27 parts of different Buddhists Your ketone diamines, 3 parts of di-n-butylamines, 342 parts of 2- propyl alcohol and 576 parts of toluene mixture in 816 parts of gained of addition carbamic acid The solution of ester prepolymer reacts 3 hours at 70 DEG C, obtains the solution of polyurethane resin.144 parts of first are added wherein Benzene and 72 parts of 2- propyl alcohol obtain polyurethane resin (adhesive resin C2) solution that solid constituent is 30%.Mw is 54, 000, Tg is -7 DEG C, acid value 3mgKOH/g.

<Adhesive resin C3>

It is added 50 in the reaction vessel for having blender, thermometer, dropper, reflux condenser and gas introduction tube Part methyl ethyl ketone, 80 DEG C are heated to when injecting nitrogen in a reservoir, and 3 parts of first were added dropwise with 1 hour at said temperatures Base acrylic acid, 32 parts of n-BMAs, 65 parts of lauryl methacrylates and 4 part 2,2 '-azobis isobutyronitriles mix It closes object and carries out polymerisation.After completion of dropwise addition, and then after being reacted 3 hours at 80 DEG C, addition keeps 1 part of azobis isobutyronitrile molten The solution of solution gained in 50 parts of methyl ethyl ketones, and then after the reaction was continued 1 hour at 80 DEG C, be cooled to room temperature.Then sharp It is diluted with methyl ethyl ketone, the acrylic resin (adhesive resin containing carboxyl for being 30% thus to obtain solid constituent C3) solution.It is -11 DEG C that Mw, which is 27,000, Tg, acid value 20mgKOH/g.

<Adhesive resin C4>

In the four-hole boiling flask for having blender, reflux condensing tube, nitrogen ingress pipe, ingress pipe and thermometer, addition 195.1 parts of polycarbonate glycol (Kuraray polyalcohol (Kuraray Polyol) C-2090), as main chain with containing anhydride group 29.2 parts of tetrabydrophthalic anhydrides (physics and chemistry West Germany (Rikacid) TH of compound：New Japan Chemical limited liability company system Make) and as solvent 350 parts of toluene, under nitrogen flowing stirring while be warming up to 60 DEG C, make its uniform dissolution.Then will The flask is warming up to 110 DEG C, reacts 3 hours.Thereafter, after being cooled to 40 DEG C, 26 parts of bisphenol A type epoxy compound (YD- are added 8125：Chemistry limited liability company of Nippon Steel manufactures：Epoxide equivalent=175g/eq) and 4 parts of triphenylphosphines as catalyst are simultaneously 110 DEG C are warming up to, is reacted 8 hours.After being cooled to room temperature, 11.56 part four as compound of the side chain containing anhydride group is added Hydrogen phthalic anhydride reacts 3 hours at 110 DEG C.After being cooled to room temperature, using toluene with solid constituent become 30% side Formula adjusts, and obtains add-on type polyester resin solution (adhesive resin C4).It is -25 DEG C that Mw, which is 15,000, Tg, and acid value is 25mgKOH/g。

<Adhesive resin C5>

In the four-hole boiling flask for having blender, reflux condensing tube, nitrogen ingress pipe, ingress pipe and thermometer, addition 54.5 parts of decanedioic acid, 5.5 parts of 5- Hydroxy M Phthalic Acids, 148.4 parts of dimer diamine " Puli's amine (Priamine) 1074 " (Japan Crow is manufactured up to (Croda Japan) limited liability company, amine value 210.0mgKOH/g) and 100 parts of ion exchange waters, stirring Until heating temperature becomes certain.Temperature is warming up to 110 DEG C after stablizing, after the outflow for confirming water, by temperature liter after 30 minutes Temperature continues dehydration when being heated up as unit of 10 DEG C every 30 minutes thereafter to 120 DEG C.Temperature reaches 230 After DEG C, the temperature is kept and the reaction was continued 3 hours, kept for 1 hour under the vacuum of about 2KPa.Thereafter, temperature is reduced, with 146 parts of toluene and 146 parts of 2- propyl alcohol dilutions, obtain polyamide (adhesive resin C5) solution.Mw is 36,000, Tg 5 DEG C, acid value 12mgKOH/g.

Furthermore Mn, Mw, Tg, epoxide equivalent, acid value and the hydroxyl valence of adhesive resin are asked according to the following method Go out.

<The measurement of Mn, Mw>

Device：GPC (gel permeation chromatograph)

Machine：Clear moral (Shodex) GPC-101 of Showa electrician (stock) company manufacture

Tubing string：The GPCKF-G+KF805L+KF803L+KF802 of Showa electrician (stock) company manufacture

Detector：Differential refractive index detector, clear moral (Shodex) RI-71 of Showa electrician (stock) company manufacture

Eluat：Tetrahydrofuran (Tetrahydrofuran, THF)

Flow：Sample side：1mL/min, with reference to side：0.5mL/min

Temperature：40℃

Sample：0.2%THF solution (100 μ L injections)

Calibration curve：12 points of the standard polystyren of the following molecular weight manufactured using Tosoh (Tosoh) (stock) company is come Make calibration curve.

F128(1.09×10⁶)、F80(7.06×10⁵)、F40(4.27×10⁵)、F20(1.90×10⁵)、F10(9.64 ×10⁴)、F4(3.79×10⁴)、F2(1.81×10⁴)、F1(1.02×10⁴)、A5000(5.97×10³)、A2500(2.63× 10³)、A1000(1.05×10³)、A500(5.0×10²)。

Baseline：Using the rising point of the initial peak of GPC curves as starting point, retention time 25 minutes (molecular weight 3, 150) peak value is not detected in place, therefore using it as terminal.Then, using the line for linking at 2 points as baseline, molecular weight is calculated.

<The measurement of Tg>

Device：The Differential Scanning Calorimeter analysis meter DSC- of Seiko instrument (Seiko Instruments) (stock) company manufacture 220C

Sample：About 10mg (is accurate to 0.1mg)

Heating rate：It is measured with 10 DEG C/min until 200 DEG C

Tg temperature：Be set as the baseline of low temperature side to high temperature side extended straight line, in the low temperature side for melting peak value Gradient reaches the temperature of the intersection point of broken line made by maximum point in curve.

<The measurement of epoxide equivalent>

It is measured according to Japanese Industrial Standards (Japanese Industrial Standards, JIS) K 7236.

<The measurement of hydroxyl valence, acid value>

It is measured according to JIS K 0070.

[dispersant (D)]

D1：Polyester and polyether dispersant containing phosphate, the dispersant for being neutralized acidic group using alkanolamine (Bi Ke chemistry The Di Sipabike (DISPER BYK) -180 of (BYK Chemie) company manufacture)

D2：Polyester and polyether dispersant (the Di Sipabi of Bi Ke chemistry (BYK Chemie) company manufacture containing phosphate Gram (DISPER BYK) -110)

D3：The polyester dispersants with aromatic carboxylic acid described in No. 2008/007776 bulletin of International Publication No.

D4：Dispersant D3 is neutralized using alkanolamine

D5：Silane coupling agent (KBM-5103 of chemical industrial company of SHIN-ETSU HANTOTAI manufacture) containing acrylic

[curing agent]

Curing agent 1：Epoxide (Ai Dike resins (AdekaResin) EP-4100, bisphenol-A system, epoxide equivalent= 190g/Eq, Ai Dike (ADEKA) company manufactures)

Curing agent 2：Aziridine cpd (Kai meter Te (Chemitite) PZ-33, Japanese catalyst Co. manufacture)

[conducting particles]

Silver coated copper：Dendritic powder (D50 grain sizes：11 μm, apply silver-colored rate：10%, BET specific surface area：0.2m2/g)

<Embodiment 1>

Using planetary-type mixer by the solution of the adhesive resin C1 of 25 parts (solid constituent be 40 mass %), 0.68 part The dispersant D1 of (solid constituent is 80 mass %), 90 parts of surface treatment copper powders (AB) (include 85.7 mass parts copper powder A1 And 4.3 mass parts ascorbic acid derivates B1) and 3.2 parts of butyl carbitol acetates mixing after, then use triple-roller mill Machine is disperseed, and conductive composition is thus prepared.The nonvolatile component of the conductive composition of gained is about 84.6%, is not waved It sends out in ingredient, surface treatment copper powder (AB) is about 89.5%, and epoxy resin is about 10%, and dispersant is about 0.5%.

<2~embodiment of embodiment 22>

The type and amount of change copper powder (A) and ascorbic acid derivates (B) similarly to Example 1, is surface-treated After copper powder (AB), the type and amount of change dispersant (D) prepare the conductive composition formed shown in 1~table of table 3.Furthermore About copper powder (AB) is surface-treated used in 2~embodiment of embodiment 22, confirm similarly to Example 1 in copper powder table There are ascorbic acid derivates (B) for face attachment.

<Embodiment 23, embodiment 24>

Similarly to Example 1, (include 10 mass parts by the solution of 25 parts of adhesive resin C1 using planetary-type mixer Adhesive resin C1), 0.68 part of dispersant D1 (including 0.54 part of nonvolatile component), 81 parts of surface treatment copper powders (AB) (including 77.1 mass parts copper powder A1 and 3.9 mass parts ascorbic acid derivates B1), 9 parts of anhydrous copper formates and 3.2 parts of diethyls two After the mixing of alcohol monobutyl ether-acetate, is then disperseed using three-roll mill, thus prepare conductive composition.The conduction of gained Property composition nonvolatile component be about 84.6%, in nonvolatile component, surface treatment copper powder (AB) be about 80.6%, asphalt mixtures modified by epoxy resin Fat is about 10%, and dispersant is about 0.5%.

<Embodiment 25, embodiment 26>

As shown in table 4, the stearylamine as copper reaction promoter is further added in the composition of embodiment 23, is carried out Operation identical with embodiment 23, thus to obtain conductive composition.

<27~embodiment of embodiment 40>

It is allocated in the way of being formed shown in each solid constituent becomes table 4, table 5, further addition is as retarder thinner Toluene-isopropanol (mass ratio 2：1) mixed solvent makes nonvolatile component concentration become 45%.It will be described mixed using disperser It closes object to stir 10 minutes, thus to obtain conductive composition.

<Comparative example 1>

As shown in table 3, conductive composition is prepared without using ascorbic acid derivates B1 and dispersant D1.

<Comparative example 2>

As shown in table 3, using dispersant D1, but conductive composition is prepared without using ascorbic acid derivates B1.

<Comparative example 3>

As shown in table 3, when copper powder A1 to be scattered in adhesive resin C1, ascorbic acid derivates B1 and dispersion are used Agent D1 and prepare conductive composition.That is, without using surface treatment copper powder (AB).

<Comparative example 4>

As shown in table 3, using surface treatment copper powder (AB), but conductive composition is prepared without using dispersant D1.

<Comparative example 5>

As shown in table 3, using surface treatment copper powder (AB), but electric conductivity is prepared using the dispersant D5 without acidic groups Composition.

<Comparative example 6, comparative example 7>

As shown in table 5, conductive composition is prepared without using ascorbic acid derivates B1.

Furthermore the dispersion of 1~comparative example of comparative example 5, mixed method are to implement similarly to Example 1, in addition, comparative example 6, the dilution and dispersion of comparative example 7, mixed method are to implement similarly to Example 27.

<The making of conductive sheet>

About 1~embodiment of embodiment 26,1~comparative example of comparative example 5, in 75 μm of gathering to benzene through sided corona treatment of thickness On dioctyl phthalate second diester film (hereinafter referred to as PET film), by the conductive composition screen painting of gained at vertical 15mm × horizontal 30mm Pattern form, be dried, heat under following either condition, obtain film thickness be about 10 μm~25 μm conductive sheet. Furthermore the thickness of conductive sheet is measured using MH-15M types analyzer (manufacture of Nikon (Nikon) company).

About 27~embodiment of embodiment 40, comparative example 6, comparative example 7, it is coated on polyimide film using bar coater, It is dried, heats under following either condition, obtain the conductive sheet that film thickness is about 5 μm~12 μm.Furthermore conductive sheet The thickness of material is measured using MH-15M types analyzer (manufacture of Nikon (Nikon) company).

Drying, heating condition are as follows.

Heating condition 1：It is dried 30 minutes in an atmosphere using 150 DEG C of baking ovens.

Heating condition 2：After carrying out 30 minutes air dryings at 80 DEG C, 2 points are carried out under air with 1MPa at 150 DEG C Clock heating pressurization compacting.Then it is taken out in slef-suppression machine, air heating in 30 minutes is carried out at 150 DEG C.

Heating condition 3：After carrying out 30 minutes air dryings at 80 DEG C, 30 are carried out under air with 1MPa at 150 DEG C Minute heating pressurization compacting.

Heating condition 4：After carrying out 2 minutes air dryings at 100 DEG C, 30 are carried out under air with 2MPa at 150 DEG C Minute heating pressurization compacting.

<Sheet resistance value after initial stage, humidity resistance experiment>

Initial stage

Within 3 hours, low-resistance meter is used in the environment of 25 DEG C, humidity 50% after conductive sheet making (loresta) four probe of tandem (LSP) of GXMCP-T610 measuring machines (manufacture of analysis company of Mitsubishi Chemical) is led to measure The sheet resistance value of electrical sheet material.

After humidity resistance experiment

After the conductive sheet of gained is separately placed 24 hours in the environment of 85 DEG C, humidity 85%, 25 DEG C, humidity are moved to In the environment of 50%, similarly operates and measure sheet resistance value.

<The calculating of volume resistivity>

The sheet resistance value and film thickness that are measured using the method are substituting in following formula and calculate electric conductivity The volume resistivity of sheet material.

Volume resistivity (Ω cm)=(surface resistivity：Ω/) × (film thickness：cm)

Furthermore about more than 1.0 × 10⁵The case where, it is considered as over range (OVER RANGE) and states and make " 1.0 × 10⁵↑”。

As indicated in 1~table of table 2, the conductive composition of 1~embodiment of embodiment 20 shows good electric conductivity And humidity resistance.

On the other hand, as shown in table 3, it is entirely free of in the comparative examples 1 of ascorbic acid derivates, comparative example 2, initial stage resistance Value just outclasses 10⁴Ω cm, it is far apart with conductive paste, conductive sheet.Though containing ascorbic acid derivates, But not in advance in the surface of copper powder is handled but is simply allocated in the dispersion with adhesive resin comparative example 3, Although initial stage resistance value becomes smaller compared with comparative example 1, comparative example 2, humidity resistance is bad.In addition, even with surface treatment Copper powder (AB) but point of comparative example 4 or use without acidic groups that dispersant (D) is not used in the dispersion with adhesive resin The comparative example 5 of powder D5 is resistance to although initial stage resistance value becomes smaller compared with comparative example 1, comparative example 2 also in the same manner as comparative example 3 Humid is bad.

Embodiment 23 containing copper precursors is compared with the embodiment 1 without copper precursors, the electric conductivity after humidity resistance experiment Reduction be inhibited.

Embodiment 21, embodiment 22, embodiment 24, embodiment 26, embodiment as shown in table 3 and table 4 through hot pressing 28, embodiment 30, embodiment 32, embodiment 34, embodiment 36, embodiment 38, embodiment 40 be compared with not repressed situation, Show that more good electric conductivity, the electric conductivity also maintain high level after humidity resistance experiment.

Even if containing copper precursors but be entirely free of ascorbic acid derivates comparative example 6 initial stage electric conductivity far away from containing The initial stage electric conductivity of the embodiment 29 of copper precursors and ascorbic acid derivates.

Even if in addition, containing copper precursors but be entirely free of the conductive pastes of ascorbic acid derivates with through the situation of hot pressing (comparative example 7), the situation (comparative example 6) without hot pressing are compared, the raising of slightly visible initial stage electric conductivity, but because humidity resistance tries It tests and electric conductivity is substantially reduced.

On the other hand, the conductive paste containing copper precursors and ascorbic acid derivates and the situation (embodiment through hot pressing 30), the situation without hot pressing (embodiment 29) is compared, and initial stage electric conductivity significantly improves, and can also be incited somebody to action after humidity resistance experiment Its electric conductivity is maintained at high level.

The conductive composition of the present invention is under air calcining, it is possible to provide even if a kind of also show well without hot pressing Electric conductivity, by hot pressing keep base material adhesion, heat-resisting moisture resistance environmental reliability conductive sheet.In addition, using The conductive composition of the present invention, which is formed by wiring circuit for example, can be suitably used for mobile phone, smart mobile phone, tablet end Touch-screen display, RFID antenna circuits, the wireless power coil of end, notes type PC etc..

Claims (9)

1. a kind of conductive composition, including surface treatment copper powder (AB), adhesive resin (C) and the dispersion with acidic groups Agent (D), wherein the surface treatment copper powder (AB) is to be attached with the following general formula (1) or general formula (2) institute on the surface of copper powder (A) Ascorbic acid of expression or derivatives thereof (B)；

General formula (1)

[changing 1]

(in general formula (1), R1 and R2 separately indicate hydrogen atom or can have the acyl group of substituent group)；

General formula (2)

[changing 2]

(in general formula (2), R11 and R12 separately indicate hydrogen atom or can have the alkyl of substituent group).

2. conductive composition according to claim 1, the ascorbic acid or derivatives thereof represented by formula of (1) (B) R1 and R2 is hydrogen atom.

3. conductive composition according to claim 1 or 2, wherein the acidity of the dispersant (D) with acidic groups Base is phosphate.

4. conductive composition according to any one of claim 1 to 3, wherein the dispersant with acidic groups (D) also there is amino.

5. conductive composition according to any one of claim 1 to 4, wherein relative to 100 mass of the copper powder (A) Part, described ascorbic acid or derivatives thereof (B) is the mass parts of 1 mass parts~30.

6. conductive composition according to any one of claim 1 to 5, wherein relative to the surface treatment copper powder (AB) 100 mass parts, the dispersant (D) with acidic groups are the mass parts of 0.1 mass parts~10.

7. conductive composition according to any one of claim 1 to 6 also contains copper precursors (Y).

8. a kind of manufacturing method of conductive composition makes the ascorbic acid represented by the following general formula (1) or general formula (2) or its spread out Biological (B) is attached to the surface of copper powder (A), obtains surface treatment copper powder (AB),

The surface treatment copper powder (AB), adhesive resin (C) and dispersant (D) with acidic groups are mixed；

General formula (1)

[changing 3]

(in general formula (1), R1 and R2 separately indicate hydrogen atom or can have the acyl group of substituent group)；

General formula (2)

[changing 4]

(in general formula (2), R11 and R12 separately indicate hydrogen atom or can have the alkyl of substituent group).

9. a kind of conductive material has base material and conductive film, wherein the conductive film is according to any in claim 1 to 7 The dried object or hardening thing of conductive composition described in.